CN102199271B - Radiation-hardenable polyurethane resin and preparation method thereof - Google Patents
Radiation-hardenable polyurethane resin and preparation method thereof Download PDFInfo
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- CN102199271B CN102199271B CN 201010130882 CN201010130882A CN102199271B CN 102199271 B CN102199271 B CN 102199271B CN 201010130882 CN201010130882 CN 201010130882 CN 201010130882 A CN201010130882 A CN 201010130882A CN 102199271 B CN102199271 B CN 102199271B
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Abstract
The invention belongs to the technical field of adiation-hardenable resins and preparations of the adiation-hardenable resins, and specifically relates to an ultraviolet (UV) hardenable polyurethane resin or an electron beam (EB) hardenable resin, and a preparation method of the UV hardenable polyurethane resin or the EB hardenable polyurethane resin. In the invention, fully biodegradable polylactic acid derivative flexible chain segments with terminal hydroxyl groups are introduced to constitutional units of a polyurethane-acrylic resin, thus biodegradable characteristics of a polyurethane resin system can be improved, and through a selection of polylactic acid derivative flexible chain segments with terminal hydroxyl groups, an environmental friendly adiation-hardenable polyurethane resin with diversified performances can be prepared, wherein structures constituting the environmental friendly adiation-hardenable polyurethane resin are expressed in the specification.
Description
Technical field
The invention belongs to radiation curing resin and preparing technical field thereof, be specifically related to a kind of Adiation-hardenable polyurethane resin and preparation method thereof.
Background technology
Polyurethane acrylate resin is as a kind of important radiation curing material, and its solidifying product is widely used in the fields such as woodwork coating, coating varnish, printing-ink with the over-all properties of excellence.Polyurethane acrylate resin is to adopt polyisocyanates, long chain diol and crylic acid hydroxy ester to be prepared from.Because polyisocyanates and long chain diol have various structures to select, synthesize by molecular designing the oligomer resin of setting performance, be therefore the maximum oligopolymer of present product grade.One of paint development direction of 21st century is to popularize pollution-free environment-friendly type coating in an all-round way.In recent years, because radiation curable aqueous urethane resin has obtained research and development widely because having the outstanding feature of environmental protection, fast setting and excellent over-all properties.Usually adopt at present and introduce carboxyl as hydrophilic radical in Adiation-hardenable polyurethane resin, then neutralize by basic cpd, thereby make Adiation-hardenable polyurethane resin have certain wetting ability.Chinese patent CN101544741A introduces sulfonic group with the method for chain extension again, thereby prepares the photocuring waterborne polyurethane resin of dual anion type after disclosing and introduce carboxyl in light-cured polyurethane resin.Yet, exist the peculiar problem of general aqueous coating system by the radiation curable coating of waterborne polyurethane resin preparation.At first be the high evaporation heat of water, make predrying not only consumed energy but also time-consuming, also may cause " instantaneous corrosion " problem for the irony base material; Next is that the high surface tension of water is brought series of problems, as to base material (particularly low surface energy person) with the wetting property of pigment is poor, easily cause crawling etc.; At last, the zero pour of water is higher than general thinner, needs to add frostproofer in transportation and storage, and water-based system easily produces mould, need add mould inhibitor, makes formula complicated.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of UV-light (UV) or electron beam (EB) polyurethane by radiation curing acrylate resin that contains biodegradable polylactic acid derivative segment is provided.
A further object of the present invention is to provide the preparation method of a kind of UV-light (UV) or electron beam (EB) polyurethane by radiation curing acrylate resin.
For solving the problems of the technologies described above, the present invention adopts following technical proposals.
UV-light of the present invention (UV) or electron beam (EB) polyurethane by radiation curing acrylate resin have following structural formula:
The number-average molecular weight of this polyurethane by radiation curing acrylate resin is 800～15000, and outward appearance is transparent clarified liq, and colourity is 30～80APHA; Odorless, tasteless, nonirritant; Contain carbon-to-carbon double bond in its structure, can be used for radiation curing.
Wherein, R
1Be the polylactic acid derivative segment (I, II, III or IV) that contains terminal hydroxy group, the structural formula of the described polylactic acid derivative that contains terminal hydroxy group is as follows:
Above-mentioned R
1M in structural formula and n represent respectively the polymerization degree, and the value of m and n is limited take the number-average molecular weight of polylactic acid derivative as 400～6000.
R
2Be the polyisocyanates segment, described polyisocyanates mainly comprises tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexyl methane diisocyanate.
R
3For containing the acrylate segment of unsaturated double-bond, the described acrylate that contains unsaturated double-bond comprises trimethylolpropane diacrylate or pentaerythritol triacrylate, or R
3For vinylformic acid hydroxyl ester-(CH
2)
n-segment, described vinylformic acid hydroxyl ester segment-(CH
2)
nIn the value of n be 2,3 or 4.
The preparation method of UV-light of the present invention (UV) or electron beam (EB) Adiation-hardenable polyurethane resin is:
With material R
2With material R
1Joining in the reactor of filling with inert gas (as nitrogen) take the ratio of mol ratio as 2: 1, add the dibutyl tin laurate as catalyzer of the total mass 0.03% of above-mentioned two kinds of materials, is 75～85 ℃ of lower stirring reactions 1～1.5 hour in temperature; Being cooled to temperature is 45～50 ℃, adds and material R
2Equimolar material R
3, stirring reaction is after 2～4 hours, then to be warming up to temperature be 90～95 ℃ of stirring reactions 0.5～1 hour, namely obtains resin product of the present invention.
Wherein, R
1For having the polylactic acid derivative that contains terminal hydroxy group of one of following structural formula:
Above-mentioned R
1M in structural formula and n represent respectively the polymerization degree, and the value of m and n is limited take the number-average molecular weight of polylactic acid derivative as 400～6000.
R
2Be polyisocyanates, it mainly comprises tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexyl methane diisocyanate.
R
3For the acrylate that contains unsaturated double-bond comprises trimethylolpropane diacrylate or pentaerythritol triacrylate, or have segment and be-(CH
2)
n-vinylformic acid hydroxyl ester, the value of n is 2,3 or 4.
The present invention has following beneficial effect: introduced the polylactic acid derivative soft segment that contains terminal hydroxy group of fully biodegradable due to the present invention in the polyurethane acrylate resin structural unit, can significantly improve the biodegradable feature of environmental protection of system; The selection of the polylactic acid derivative segment by containing terminal hydroxy group simultaneously can prepare the radiation curing feature of environmental protection urethane resin of the diversified performance with said structure.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment; it is important to point out; following examples can not be interpreted as the restriction to the invention protection domain; those skilled in the art to some nonessential improvement and adjustment that the present invention makes, must belong to protection scope of the present invention according to the foregoing invention content.
Embodiment 1
In the dry four-hole boiling flask of agitator, thermometer, reflux condensing tube and nitrogen ingress pipe is housed, add tolylene diisocyanate and the polylactic acid derivative (number-average molecular weight is 2000) with aforementioned structure I, tolylene diisocyanate: the mol ratio with polylactic acid derivative of aforementioned structure I is 2: 1, add the catalyzer dibutyl tin laurate, the quality of catalyzer is 0.03% of tolylene diisocyanate and the polylactic acid derivative total mass with aforementioned structure I; Be warming up to 80 ℃ of stirring reactions 1 hour; Then be cooled to 45 ℃, add and the equimolar Hydroxyethyl acrylate of tolylene diisocyanate constant temperature stirring reaction 3 hours; Be warming up at last 95 ℃ of stirring reactions 0.5 hour, be down to room temperature, discharging.The viscosity of measuring the gained resin is 15000mPas (60 ℃, the Brookfield rotational viscosimeter that U.S. Bo Lefei company produces); Colourity is 30APHA (German Luo Weibang company produce ET7240 determination of colority instrument); Adopt UV to solidify (exposure energy 1000W/cm, adding with respect to resin quality is that the Darocur 1173 of 3% Ciba company is as light trigger), the tensile strength of cured film (60 μ m are thick) is 1600psi, and elongation is 126%, and second-order transition temperature is-38 ℃.The number-average molecular weight of described resin is 7000.
Embodiment 2
In the dry four-hole boiling flask of agitator, thermometer, reflux condensing tube and nitrogen ingress pipe is housed, add hexamethylene diisocyanate and the polylactic acid derivative (number-average molecular weight is 400) with aforementioned structure II, hexamethylene diisocyanate: the mol ratio with polylactic acid derivative of aforementioned structure II is 2: 1, add the catalyzer dibutyl tin laurate, the quality of catalyzer is 0.03% of hexamethylene diisocyanate and the polylactic acid derivative total mass with aforementioned structure II; Be warming up to 85 ℃ of stirring reactions 1.5 hours; Then be cooled to 50 ℃, add and the equimolar Propylene glycol monoacrylate of hexamethylene diisocyanate constant temperature stirring reaction 2 hours; Be warming up at last 90 ℃ of stirring reactions 0.5 hour, be down to room temperature, discharging.The viscosity of measuring the gained resin is 8600mPas (60 ℃, the Brookfield rotational viscosimeter that U.S. Bo Lefei company produces); Colourity 50APHA (German Luo Weibang company produce ET7240 determination of colority instrument); Adopt UV to solidify (exposure energy 1000W/cm, adding with respect to resin quality is that the Darocur 1173 of 3% Ciba company is as light trigger), the tensile strength of cured film (60 μ m are thick) is 420psi, and elongation is 260%, and second-order transition temperature is-39 ℃.The number-average molecular weight of described resin is 800.
Embodiment 3
In the dry four-hole boiling flask of agitator, thermometer, reflux condensing tube and nitrogen ingress pipe is housed, add isophorone diisocyanate and the polylactic acid derivative (number-average molecular weight is 1000) with aforementioned structure III, isophorone diisocyanate: the mol ratio with polylactic acid derivative of aforementioned structure III is 2: 1, add the catalyzer dibutyl tin laurate, the quality of catalyzer is 0.03% of isophorone diisocyanate and the polylactic acid derivative total mass with aforementioned structure III; Be warming up to 80 ℃ of stirring reactions 1 hour; Then be cooled to 45 ℃, add and the equimolar vinylformic acid hydroxy butyl ester of isophorone diisocyanate, constant temperature stirring reaction 3 hours; Be warming up at last 95 ℃ of stirring reactions 1 hour, be down to room temperature, discharging.The viscosity of measuring the gained resin is 10800mPas (60 ℃, the Brookfield rotational viscosimeter that U.S. Bo Lefei company produces); Colourity 65APHA (German Luo Weibang company produce ET7240 determination of colority instrument); Adopt EB to solidify (radiation dose 60kGy), the tensile strength of cured film (60 μ m are thick) is 920psi, and elongation is 180%, and second-order transition temperature is-35 ℃.The number-average molecular weight of described resin is 2000.
Embodiment 4
In the dry four-hole boiling flask of agitator, thermometer, reflux condensing tube and nitrogen ingress pipe is housed, add dicyclohexyl methane diisocyanate and the polylactic acid derivative (number-average molecular weight is 4000) with aforementioned structure IV, dicyclohexyl methane diisocyanate: the mol ratio with polylactic acid derivative of aforementioned structure IV is 2: 1, add the catalyzer dibutyl tin laurate, the quality of catalyzer is 0.03% of dicyclohexyl methane diisocyanate and the polylactic acid derivative total mass with aforementioned structure IV; Be warming up to 80 ℃ of stirring reactions 1.5 hours; Then be cooled to 45 ℃, add and the equimolar pentaerythritol triacrylate of dicyclohexyl methane diisocyanate constant temperature stirring reaction 4 hours; Be warming up at last 95 ℃ of stirring reactions 0.5 hour, be down to room temperature, discharging.The viscosity of measuring the gained resin is 26000mPas (60 ℃, the Brookfield rotational viscosimeter that U.S. Bo Lefei company produces); Colourity 60APHA (German Luo Weibang company produce ET7240 determination of colority instrument); Adopt EB to solidify (radiation dose 60kGy), the tensile strength of cured film (60 μ m are thick) is 2100psi, and elongation is 160%, and second-order transition temperature is-32 ℃.The number-average molecular weight of described resin is 13500.
Embodiment 5
In the dry four-hole boiling flask of agitator, thermometer, reflux condensing tube and nitrogen ingress pipe is housed, add diphenylmethanediisocyanate and the polylactic acid derivative (number-average molecular weight is 6000) with aforementioned structure IV, diphenylmethanediisocyanate: the polylactic acid derivative mol ratio with aforementioned structure IV is 2: 1, add the catalyzer dibutyl tin laurate, the quality of catalyzer is 0.03% of diphenylmethanediisocyanate and the polylactic acid derivative total mass with aforementioned structure IV; Be warming up to 80 ℃ of stirring reactions 1.5 hours; Then be cooled to 45 ℃, add and the equimolar trimethylolpropane diacrylate of diphenylmethanediisocyanate constant temperature stirring reaction 4 hours; Be warming up at last 95 ℃ of stirring reactions 1 hour, be down to room temperature, discharging.The viscosity of measuring the gained resin is 28000mPas (60 ℃, the Brookfield rotational viscosimeter that U.S. Bo Lefei company produces); Colourity 50APHA (German Luo Weibang company produce ET7240 determination of colority instrument); Adopt EB to solidify (radiation dose 60kGy), the tensile strength of cured film (60 μ m are thick) is 2600psi, and elongation is 130%, and second-order transition temperature is-30 ℃.The number-average molecular weight of described resin is 15000.
Claims (4)
1. a polyurethane by radiation curing acrylate resin, is characterized in that, this resin has following structural formula:
Wherein, R
1For containing the polylactic acid derivative segment of terminal hydroxy group, the described polylactic acid derivative that contains terminal hydroxy group has one of following structural formula:
Above-mentioned R
1M in structural formula and n represent respectively the polymerization degree, and the value of m and n is limited take the number-average molecular weight of polylactic acid derivative as 400～6000;
R
2Be the polyisocyanates segment, described polyisocyanates is tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexyl methane diisocyanate;
R
3For containing the acrylate segment of unsaturated double-bond, the described acrylate that contains unsaturated double-bond is trimethylolpropane diacrylate or pentaerythritol triacrylate, or R
3For vinylformic acid hydroxyl ester-(CH
2)
n-segment, described vinylformic acid hydroxyl ester segment-(CH
2)
nIn the value of n be 2,3 or 4.
2. polyurethane by radiation curing acrylate resin according to claim 1, it is characterized in that: the number-average molecular weight of described resin is 800～15000, colourity is 30～80APHA.
3. the preparation method of an Adiation-hardenable polyurethane resin according to claim 1 and 2 is characterized in that:
With material R
2With material R
1Joining in the reactor of filling with inert gas take the ratio of mol ratio as 2: 1, add the dibutyl tin laurate as catalyzer of the total mass 0.03% of above-mentioned two kinds of materials, is 75～85 ℃ of lower stirring reactions 1～1.5 hour in temperature; Being cooled to temperature is 45～50 ℃, adds and material R
2Equimolar material R
3, stirring reaction is after 2～4 hours, then to be warming up to temperature be 90～95 ℃ of stirring reactions 0.5～1 hour, obtains the polyurethane by radiation curing acrylate resin product of following structure;
Wherein, R
1For having the polylactic acid derivative that contains terminal hydroxy group of one of following structural formula:
Above-mentioned R
1M in structural formula and n represent respectively the polymerization degree, and the value of m and n is limited take the number-average molecular weight of polylactic acid derivative as 400～6000;
R
2Be tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexyl methane diisocyanate;
R
3Be trimethylolpropane diacrylate or pentaerythritol triacrylate, or have segment and be-(CH
2)
n-vinylformic acid hydroxyl ester, the value of n is 2,3 or 4.
4. method according to claim 3, it is characterized in that: the number-average molecular weight of described resin is 800～15000, colourity is 30～80APHA.
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| CN 201010130882 CN102199271B (en) | 2010-03-22 | 2010-03-22 | Radiation-hardenable polyurethane resin and preparation method thereof |
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| CN102199271B true CN102199271B (en) | 2013-05-22 |
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| CN103030767A (en) * | 2012-12-07 | 2013-04-10 | 江苏三木集团有限公司 | Degradable radiation-curable polyurethane acrylate oligomer and preparation method thereof |
| CN103483536B (en) * | 2013-08-27 | 2016-08-10 | 陕西科技大学 | A kind of preparation method of use for synthetic leather no-solvent ultraviolet curing polyurethane |
| CN103694880B (en) * | 2013-12-30 | 2015-08-26 | 浙江荣泰科技企业有限公司 | The preparation method of waterborne one-component polyurethane paint with low viscosity |
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| CN104017170B (en) * | 2014-06-18 | 2016-07-06 | 湖南松井新材料有限公司 | The six phosphate modified acrylates of degree of functionality, preparation method, the ultraviolet-cured paint with this resin and this paint coating process |
| CN105924604B (en) * | 2016-05-18 | 2018-09-25 | 湖南科技大学 | A kind of preparation method and product of degradable aqueous polyurethane coating |
| CN106519161A (en) * | 2016-10-25 | 2017-03-22 | 深圳光华伟业股份有限公司 | Light-cured resin prepolymer, light-cured resin and preparation methods of light-cured resin prepolymer and light-cured resin |
| KR102241367B1 (en) * | 2018-01-05 | 2021-04-15 | 주식회사 엘지화학 | Block copolymer |
| KR102286545B1 (en) * | 2018-01-05 | 2021-08-04 | 주식회사 엘지화학 | Block copolymer |
| CN109400844A (en) * | 2018-09-19 | 2019-03-01 | 江苏三木化工股份有限公司 | A kind of biology base photocurable prepolymer and preparation method thereof |
| KR20200115166A (en) | 2019-03-26 | 2020-10-07 | 주식회사 엘지화학 | Tri block copolymer and process for preparation thereof |
| CN111057203B (en) * | 2019-12-31 | 2022-03-22 | 北京松井工程技术研究院有限公司 | Silicon-fluorine polyurethane acrylic resin and preparation method and application thereof |
| KR102334643B1 (en) * | 2021-04-09 | 2021-12-02 | 주식회사 엘지화학 | Block copolymer |
| CN114835860A (en) * | 2022-03-29 | 2022-08-02 | 深圳锐沣科技有限公司 | Degradable DLP3D printing facing resin |
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